CN100480345C - Fluorinated low surface energy cathode electrophoresis paint and preparation method thereof - Google Patents
Fluorinated low surface energy cathode electrophoresis paint and preparation method thereof Download PDFInfo
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- CN100480345C CN100480345C CNB2004100776729A CN200410077672A CN100480345C CN 100480345 C CN100480345 C CN 100480345C CN B2004100776729 A CNB2004100776729 A CN B2004100776729A CN 200410077672 A CN200410077672 A CN 200410077672A CN 100480345 C CN100480345 C CN 100480345C
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Abstract
A fluoric cathode electrophoresis paint with low surface energy is applied by electrophoretic coating and features high decorative and anticorrosive effects. Its preparing process includes such steps as proportionally mixing electrophoretic fluoric acrylic resin with acrylic resin or epoxy resin, stirring, diluting with deionized water, and regulating pH value by organic acid.
Description
Technical field
The present invention relates to a kind of electrophoretic paint technology, low surface energy cathode electrophoresis paint of particularly a kind of end table unification and preparation method thereof.
Background technology
Because most of organic solvent is inflammable, poisonous, and human health and environment are had detrimentally affect, water-borne coatings particularly electrocoating paint (electrophoretic paint) has obtained fast development in the seventies in 20th century.Compare with other coating processs, electrodeposition coating has following characteristics: the 1. thickness homogeneous of paint film, and compactness is good, excellent corrosion resistance; 2. the utilization ratio height of coating is generally 95%～99%; 3. the permeability ratio even coating ability of the various piece of workpiece (promptly to) height is particularly suitable for applying complex-shaped, corrosion-resistant demanding workpiece; 4. volatile organic matter (VOC) and hazardous air pollutants (HAPs) content are low, and is little to environmental damage, belongs to green environmental friendly coatings.Therefore cathode electrophoresis dope obtains to use widely in all conglomeraties such as automotive industry, household electrical appliance, instrument, building materials, toy.
Most electrophoretic paints can only obtain single anticorrosion or decorative coveringn.But single coating is subjected to the restriction of thickness, fraction of coverage etc., has influenced the practical application of single layer coating.Recently, cathode electrophoresis dope develops to the direction (can obtain possessing the coating of priming paint and finish paint function simultaneously) of " end table unification " both at home and abroad.Cathode electrophoresis dope forms the bilayer structure that component has graded after galvanic deposit once or twice, curing, can not only give coating inside and outside two-layer different function, and can give full play to various resin Compositions excellent specific property separately.
Along with the continuous development and progress of electrophoretic paint technology, people are to the demands for higher performance of coating.Japan succeeds in developing the vinyl fluoride-vinyl ether co-polymer that can be scattered in the water in the eighties, and attempts this fluorine resin is applied to the anode electrophoresis dope field, obtains the ability cathode electrophoresis coating of low surface energy.But the synthetic needs of vinyl fluoride-vinyl ether co-polymer are used autoclave, and copolyreaction is alternating copolymerization, and the multipolymer after the modification is solvable in organic solvent commonly used, and the preparation water-base resin is difficulty comparatively, and are difficult to obtain the coating of end table unification.
Summary of the invention
The objective of the invention is to remedy the defective of prior art, the table unification of a kind of end is provided and have the low surface energy effect low surface energy cathode electrophoresis paint the preparation method, the paint film that the electrophoretic paint that obtains prepares behind a cathode electro-coating has excellent ornamental, preservative property and low surface energy.
Another object of the present invention is to provide the low surface energy cathode electrophoresis paint of described method preparation.
The preparation method of low surface energy cathode electrophoresis paint of the present invention comprises: with solid content is that the fluorine-containing ability cathode electrophoresis resin of 50～80% quality, epoxy ability cathode electrophoresis resin or vinylformic acid ability cathode electrophoresis resin, solidifying agent and the solubility promoter that solid content is 50～80% quality mix, add the deionized water dilution, regulator solution pH value to 4.0～6.5;
The weight ratio of described fluorine-containing ability cathode electrophoresis resin, epoxy ability cathode electrophoresis resin or vinylformic acid ability cathode electrophoresis resin, deionized water is 10～30:10～30:30～70.
Described fluorine-containing ability cathode electrophoresis resin is by acrylate monomer and other acrylate monomer or styrene copolymerized the obtaining of fluorine-containing carbon side chain.
Described epoxy ability cathode electrophoresis resin is the amine affixture of bisphenol A type epoxy resin, and the epoxy equivalent (weight) of Resins, epoxy is in 200～4000 scopes.
Shown in several by in (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) isobutyl acrylate, (methyl) Ethyl acrylate, (methyl) dodecylacrylate, (methyl) Hydroxyethyl acrylate, (methyl) Propylene glycol monoacrylate, vinylbenzene, (methyl) dimethylaminoethyl acrylate of acrylic acid ability cathode electrophoresis resin by the poly-preparation of free radical benzene.
Described solidifying agent is the terpolycyantoamino-formaldehyde resin of pure etherificate or the polyisocyanate crosslinker of different organism sealing, and hardener dose is 5～20% quality of cathode resin total amount.
Described solubility promoter adopts methyl alcohol, ethanol, Virahol, butanols, acetone, butanone, tetrahydrofuran (THF), ritalin, vinyl acetic monomer, N-BUTYL ACETATE, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol ether, ethylene glycol monobutyl ether, glycol methyl ether acetate, ethylene glycol ether acetate or 1-Methoxy-2-propyl acetate etc., and its consumption accounts for 15～25% quality of ability cathode electrophoresis resin.
Use organic acid for adjusting pH value, described organic acid adopts formic acid, acetate, oxyacetic acid, methanesulfonic, ethane sulfonic acid, propane sulfonic acid, hydroxyethanesulfonic acid or hydroxypropanesulfonic acid.
The preparation of electrophoretic paint of the present invention is carried out in universal high speed dispersion machine or special-purpose emulsifying machine.
The present invention has following advantage with respect to prior art: the coating that can obtain low surface energy, high-decoration and preservative property through cathode electro-coating.This cathode electrophoresis dope ph value of emulsion is 4.0～6.5, and specific conductivity is 1500～3000 μ s/cm, and electrophoretic voltage 50～200V, electrophoresis temperature are 20～40 ℃, and electrophoresis time is 1～5 minute; Paint film solidified 10～30 minutes at 130～180 ℃; It is evenly smooth smooth to make paint film appearance, and thickness is adjustable in 15～40 μ m, the resistance to acids and bases excellence, and static surface contact angle water is measured as 60～90 ° (size of contact angle is to weigh surface energy standard the most easily, and contact angle is big, and then surface energy is low).In addition, table unification low surface energy cathode electrophoresis paint in the end of the present invention has high permeability ratio and stable electrophoresis.
Description of drawings
Fig. 1 is the stereoscan photograph of fluorine-containing ability cathode electrophoresis resin and epoxy ability cathode electrophoresis resin compounded cataphoretic coating.
Fig. 2 is the stereoscan photograph of epoxy ability cathode electrophoresis resin cataphoretic coating.
Embodiment
Embodiment 1
(1) prescription
Title specification parts by weight
Fluorine-containing cathode electrophoresis dope resin solid content is 60%.100
Vinylformic acid cathode electrophoresis dope resin solid content is 60%.150
The butyl alcohol etherified melamine-formaldehyde resin solid content is 99%.50
Deionized water specific conductivity＜15 μ s/cm 700
(2) preparation technology
Earlier fluorine-containing and vinylformic acid ability cathode electrophoresis resin stoste and butyl alcohol etherified melamine-formaldehyde resin are stirred with high speed dispersor, join in the electrophoresis chamber, slowly add the deionized water dilution, regulate the pH value to 5.0 of tank liquor with acetate, stirred 24 hours with high speed dispersor, obtain directly to carry out the coating emulsion of electrophoresis experiment.
Ability cathode electrophoresis technology is adopted in test, and the coated article iron plate is hung on negative electrode, and anode is a stainless steel substrates; The coated article iron plate needed to transfer a series of operations such as (colloid peptide), washing, phosphatization to carry out pre-treatment through oil removing, washing, rust cleaning, washing, neutralization, table before galvanic deposit.Electrophoretic voltage is 150V, and electrodeposition time is 3 minutes.After electrophoresis finished, taking-up had the iron plate elder generation immersion tap water of filming and removes the lacquer liquid that remains in the surface, uses distilled water flushing again, solidifies 30 minutes at 180 ℃ afterwards.It is evenly smooth smooth to make paint film appearance, holiday few (see the stereoscan photograph of Fig. 1, stereoscan photograph Fig. 2 that the vinylformic acid ability cathode electrophoresis is filmed under attached the same terms is so that contrast), thickness is about 30 μ m, the acid-proof alkaline excellence, the water surface contact angle is 84 °, surface energy is lower.This electrophoretic paint paint film property is listed in table 1.
The performance of table 1 electrodeposited paint film
Embodiment 2
(1) prescription
Title specification parts by weight
Fluorine-containing cathode electrophoresis dope resin solid content is 60%.50
Epoxy cathode electrophoresis dope resin solid content is 30%.200
The butyl alcohol etherified melamine-formaldehyde resin solid content is 99%.50
Deionized water specific conductivity＜15 μ s/cm 700
(2) preparation technology
With technology among the embodiment 1.It is evenly smooth smooth to make paint film appearance, and about thickness 30 μ m, the water surface contact angle is 78～80 °.Other performance index are close with embodiment 1.
Embodiment 3
(1) prescription
Title specification parts by weight
Fluorine-containing cathode electrophoresis dope resin solid content is 60%.50
Vinylformic acid cathode electrophoresis dope resin solid content is 60%.215
Methyl ethyl ketoxime blocked polyisocyanates solid content is 80%.35
Deionized water specific conductivity＜15 μ s/cm 700
(2) preparation technology
With technology among the embodiment 1.But the film curing temperature is 160 ℃.It is evenly smooth smooth to make paint film appearance, and about thickness 25 μ m, the water surface contact angle is 78～80 °.Other performance index are close with embodiment 1.
Embodiment 4
(1) prescription
With prescription among the embodiment 1.
(2) preparation technology
With technology among the embodiment 1, but electrophoretic voltage is adjusted to 50V.It is evenly smooth smooth to make paint film appearance, and thickness is about 20 μ m, and the water surface contact angle is 78～80 °, and other performance index are close with embodiment 1.
Embodiment 5
(1) prescription
Title specification parts by weight
Fluorine-containing cathode electrophoresis dope resin solid content is 60%.50
Vinylformic acid cathode electrophoresis dope resin solid content is 60%.150
The butyl alcohol etherified melamine-formaldehyde resin solid content is 99%.50
Deionized water specific conductivity＜15 μ s/cm 750
(2) preparation technology
With technology among the embodiment 1, but electrophoretic paint resin emulsion pH value is adjusted to 4.5 with acetate.It is evenly smooth smooth to make paint film appearance, and thickness is about 20 μ m, and the water surface contact angle is 78～80 °, and other performance index are close with embodiment 1.
The technical indicator of end table unification low surface energy cathode electrophoresis paint emulsion of the present invention is:
| Solids content | 20～40％ |
| The pH value | 4.0～6.5 |
| Viscosity | 100～400cps(25±1℃) |
| Specific conductivity | 1500～3000μs/cm(25±1℃) |
Claims (5)
1, a kind of preparation method of low surface energy cathode electrophoresis paint, it is characterized in that comprising: with solid content is that the fluorine-containing ability cathode electrophoresis resin of 50～80% quality, epoxy ability cathode electrophoresis resin or vinylformic acid ability cathode electrophoresis resin, solidifying agent and the solubility promoter that solid content is 50～80% quality mix, add the deionized water dilution, regulator solution pH value to 4.0～6.5;
The weight ratio of described fluorine-containing ability cathode electrophoresis resin, epoxy ability cathode electrophoresis resin or vinylformic acid ability cathode electrophoresis resin, deionized water is 10～30:10～30:30～70;
Described fluorine-containing ability cathode electrophoresis resin is by acrylate monomer and other acrylic ester monomer or styrene copolymerized the obtaining of fluorine-containing carbon side chain;
Described epoxy ability cathode electrophoresis resin is the amine affixture of bisphenol A type epoxy resin, and the epoxy equivalent (weight) of Resins, epoxy is in 200～4000 scopes;
Described vinylformic acid ability cathode electrophoresis resin is prepared by free-radical polymerized by several in (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) isobutyl acrylate, (methyl) Ethyl acrylate, (methyl) dodecylacrylate, (methyl) Hydroxyethyl acrylate, (methyl) Propylene glycol monoacrylate, vinylbenzene, (methyl) dimethylaminoethyl acrylate.
2, the preparation method of low surface energy cathode electrophoresis paint according to claim 1, it is characterized in that described solidifying agent is the terpolycyantoamino-formaldehyde resin of pure etherificate or the polyisocyanate crosslinker of different organism sealing, hardener dose is 5～20% quality of ability cathode electrophoresis resin total amount.
3, the preparation method of low surface energy cathode electrophoresis paint according to claim 1 and 2, it is characterized in that described solubility promoter adopts methyl alcohol, ethanol, Virahol, butanols, acetone, butanone, tetrahydrofuran (THF), ritalin, vinyl acetic monomer, N-BUTYL ACETATE, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol ether, ethylene glycol monobutyl ether, glycol methyl ether acetate, ethylene glycol ether acetate or 1-Methoxy-2-propyl acetate, its consumption accounts for 15～25% quality of ability cathode electrophoresis resin.
4, the preparation method of low surface energy cathode electrophoresis paint according to claim 3, it is characterized in that using organic acid for adjusting pH value, described organic acid adopts formic acid, acetate, oxyacetic acid, methanesulfonic, ethane sulfonic acid, propane sulfonic acid, hydroxyethanesulfonic acid or hydroxypropanesulfonic acid.
5, the low surface energy cathode electrophoresis paint of the described method preparation of claim 1.
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| CNB2004100776729A CN100480345C (en) | 2004-12-28 | 2004-12-28 | Fluorinated low surface energy cathode electrophoresis paint and preparation method thereof |
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| CNB2004100776729A CN100480345C (en) | 2004-12-28 | 2004-12-28 | Fluorinated low surface energy cathode electrophoresis paint and preparation method thereof |
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| CN100480345C true CN100480345C (en) | 2009-04-22 |
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Families Citing this family (15)
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| DE502008001312D1 (en) * | 2008-04-04 | 2010-10-28 | Fraunhofer Ges Forschung | Formulation for the semi-permanent protection of surfaces and their use |
| CN101993576B (en) * | 2010-11-04 | 2012-01-25 | 安吉万国涂料有限公司 | Resin emulsion for hydrophobic cathode electrophoretic coating as well as preparation method and application thereof |
| CN102296340A (en) * | 2011-09-09 | 2011-12-28 | 福清永动力弹簧科技有限公司 | Electrophoresis process for spring |
| CN103333596B (en) * | 2013-06-24 | 2015-09-23 | 浩力森涂料（上海）有限公司 | Fluorinated silicone modified acrylic cathodic electrophoretic coating of a kind of automatically cleaning and preparation method thereof |
| CN103554350B (en) * | 2013-11-13 | 2015-12-02 | 深圳市志邦科技有限公司 | The preparation method of organosilicon modified crylic acid resin |
| CN103601838B (en) * | 2013-11-13 | 2015-12-02 | 深圳市志邦科技有限公司 | The preparation method of the special fluorocarbon resin of fluorine-containing electrocoating paint |
| CN104404603A (en) * | 2014-11-05 | 2015-03-11 | 柳州金茂机械有限公司 | Rear vehicle frame coating technology |
| CN105670002A (en) * | 2014-11-18 | 2016-06-15 | 立邦涂料（天津）有限公司 | Production process of resin used in electrophoretic paint |
| CN104725910A (en) * | 2015-03-10 | 2015-06-24 | 铜陵市陵阳化工有限责任公司 | Cathode electrophoresis paint with antistatic and antifreezing functions and manufacturing method thereof |
| CN104987761B (en) * | 2015-07-29 | 2017-06-16 | 湖南省霖辉高新材料科技有限公司 | A kind of UV cathode electrodip paintings and its coating process |
| CN106243311A (en) * | 2016-08-03 | 2016-12-21 | 广东科德环保科技股份有限公司 | A kind of aqueous epoxy resin emulsion and preparation method thereof, cathode electrophoresis dope |
| CN106634384A (en) * | 2016-10-01 | 2017-05-10 | 浙江科技学院 | Preparation method of cation acrylate resin of cathode electrophoresis coating |
| CN106883690A (en) * | 2017-04-06 | 2017-06-23 | 广德瑞邦涂料有限公司 | A kind of inventive thick film paste solvent-borne type electrophoretic paint |
| CN108912949A (en) * | 2018-05-25 | 2018-11-30 | 河北晨阳工贸集团有限公司 | A kind of cathode electrophoresis dope and preparation method thereof suitable for gas range |
| CN113684519A (en) * | 2021-08-23 | 2021-11-23 | 泰兴市华盛银洋新材料科技有限公司 | Process for machining micro-arc oxidized workpiece by vacuum sputtering and electrophoretic coating technology |
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Assignee: Hangzhou Jihua Polymer Material Co., Ltd. Assignor: South China University of Technology Contract record no.: 2010330001106 Denomination of invention: Fluorinated low surface energy cathode electrophoresis paint and its preparation method Granted publication date: 20090422 License type: Exclusive License Open date: 20050810 Record date: 20100611 |
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